WO2014074234A1 - Procédé pour améliorer le durcissement d'un revêtement pour un article revêtu dans une composition de revêtement par électrodéposition contaminée par du phosphate et composition de revêtement par électrodéposition - Google Patents

Procédé pour améliorer le durcissement d'un revêtement pour un article revêtu dans une composition de revêtement par électrodéposition contaminée par du phosphate et composition de revêtement par électrodéposition Download PDF

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Publication number
WO2014074234A1
WO2014074234A1 PCT/US2013/061399 US2013061399W WO2014074234A1 WO 2014074234 A1 WO2014074234 A1 WO 2014074234A1 US 2013061399 W US2013061399 W US 2013061399W WO 2014074234 A1 WO2014074234 A1 WO 2014074234A1
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WIPO (PCT)
Prior art keywords
coating composition
bismuth
electrocoat
zirconium silicate
coating
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PCT/US2013/061399
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English (en)
Inventor
Robert D. Schiller
Kevin M. Schock
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Basf Coatings Gmbh
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Publication date
Application filed by Basf Coatings Gmbh filed Critical Basf Coatings Gmbh
Priority to EP13776618.4A priority Critical patent/EP2917293B1/fr
Priority to CA2883990A priority patent/CA2883990A1/fr
Priority to CN201380057953.5A priority patent/CN104769051B/zh
Priority to JP2015541766A priority patent/JP6375304B2/ja
Priority to MX2015003384A priority patent/MX2015003384A/es
Priority to US14/441,430 priority patent/US20150267315A1/en
Publication of WO2014074234A1 publication Critical patent/WO2014074234A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/10—Electrophoretic coating characterised by the process characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • the invention concerns organic electrocoat coating compositions and methods, particularly those that are part of a coating process that includes a phosphate pretreatment of a metal article before the article is electrocoated.
  • Industrial coating of metal articles that will be used in corrosive environments may include application of one or more inorganic and organic treatments and coatings.
  • Painting systems ("paint shops") in automotive assembly plants are large, complex, and expensive.
  • Metal automotive vehicle bodies (the
  • body-in-white and parts, for instance, are given a many-step treatment including cleaning in one or more cleaning baths or spray tanks, application of an aqueous phosphate coating material as a metal pretreatment step in a phosphating bath, then various rinses and additional finishing treatments.
  • a treatment is described in Claffey, U.S. Patent No. 5,868,820, for example.
  • the phosphating pre-treatment steps are undertaken to improve corrosion resistance of the metal and adhesion of subsequent coatings to the metal.
  • Electrocoat baths usually comprise an aqueous dispersion or emulsion of a principal film- forming resin having ionic stabilization in water or a mixture of water and organic cosolvent.
  • the electrocoat compositions are formulated to be curable (thermosetting) compositions. This is usually accomplished by emulsifying with the principal film-forming resin a crosslinking agent that can react with functional groups on the principal resin under appropriate conditions, such as with the application of heat, and so cure the coating.
  • Typical electrocoat coating compositions for coating automotive vehicle bodies and parts contain epoxy resin as the principle resin and blocked polyisocyanate as the crosslinker.
  • coating material containing the ionically- charged resin having a relatively low molecular weight is deposited onto a conductive substrate by submerging the substrate in the electrocoat bath and then applying an electrical potential between the substrate and a pole of opposite charge, for example, a stainless steel electrode.
  • the charged coating material migrates to and deposits on the conductive substrate.
  • the coated substrate is then heated to cure or crosslink the coating.
  • These electrocoat coating compositions further include a catalyst for the curing reaction between the epoxy resin and the polyisocyanate to make it possible to cure the deposited coating in a time and at a temperature that are commercially reasonable.
  • Yasuoka et al, US Patent No. 5,330,839 describes a blocked isocyanate group-containing electrocoating composition comprising at least one dialkyltin aromatic carboxylate and at least one bismuth or zirconium compound as a combined curing catalyst.
  • Hiraki et al., EP 1 046 683 describes a cationically electrodepositable paint having very low organic solvent content.
  • the paint includes a corrosion preventative pigment that may be selected from a variety of metal compounds.
  • Organic tin compounds can be added.
  • Kawaraya et al, US Patent No. 7,625,477 describes an electrodeposition paint comprising particles of at least one metallic compound selected from bismuth hydroxide, zirconium compound and tungsten compound which is said to excel in corrosion resistance. Organotin compounds may be included.
  • the method may include determining a concentration of phosphate ions in the coating composition and, if the concentration of phosphate ions in the coating composition is above about 50 ppm, preferably above about 100 ppm, based on total weight of the electrocoat coating composition ("bath"), adding zirconium silicate to the coating composition to improve cure response of the coating composition. A reduction in cure response of coatings electrodeposited from the bath may be observed, then the concentration of phosphate ions in the bath determined and zirconium silicate added in response to a measured concentration of the phosphate ions.
  • an aqueous coating composition having a cathodically electrodepositable binder.
  • the binder has a principal resin and a blocked polyisocyanate crosslinker capable of reacting with the principal resin during cure.
  • the coating composition is made by including zirconium silicate and a catalyst consisting essentially of bismuth compounds and mixtures of bismuth compounds.
  • the aqueous coating composition provides the advantages of a bismuth catalyst while being protected against the poisoning effect of phosphate ions on the bismuth catalyst during cure of a coating electrodeposited from the coating composition.
  • an aqueous coating composition again having a cathodically electrodepositable binder, the binder having a principal resin and a blocked polyisocyanate crosslinker, in which the coating composition includes zirconium silicate and at least one bismuth compound other than bismuth hydroxide.
  • the coating composition is free of tin compounds and free of bismuth hydroxide.
  • Still further disclosed is a method of coating an electrically conductive substrate, such as a metal automotive body or part, by placing the electrically conductive substrate in one of the aqueous coating compositions described above.
  • the substrate is attached as one electrode and there a second electrode is provided in the aqueous electrocoat coating composition, then a current is passed through the aqueous coating composition to deposit a coating layer onto the electrically conductive substrate.
  • the binder is cathodically electrodepositable and the electrically conductive substrate is attached as a cathode when the current is passed through the aqueous coating composition.
  • the deposited coating layer may then be cured to a cured coating layer.
  • the polyisocyanate crosslinker reacts with the principal resin to form a crosslinked binder in the cured coating layer, a reaction that catalyzed by the bismuth compound or compounds.
  • Subsequent coating layers may be applied on the electrodeposited coating layer, and the layers may be cured individually as each is applied or two or more layers may be cured together.
  • the electrodeposited coating layer may be a primer layer and other layers such as an optional spray-applied primer surfacer and a topcoat layer or topcoat layers (e.g., a colored basecoat layer and a clearcoat layer) may be applied over the electrodeposited coating layer. All coating layers may be cured together, or the electrodeposited coating layer and primer layer, may be cured together or individually and the topcoat layer or topcoat layers cured together (if more than one topcoat layer) or individually.
  • contaminated with phosphate ions is treated by adding zirconium silicate to the coating composition to prevent the phosphate ions from interfering with cure of a coating electrodeposited from the coating composition.
  • the zirconium silicate may be added in an aqueous dispersion in which the zirconium silicate is dispersed with a dispersant or with a dispersing resin (also known as a grinding resin).
  • a dispersant or dispersing resin also known as a grinding resin.
  • Suitable, nonlimiting examples of dispersants or dispersing resins include those described in Carpenter et al, U.S. Patents No. 5527614 and 5536776; Rueter et al., U.S. Patent No. 6,951,602; Hsieh et al, U.S. Patent No. 6,288,176; Honig et al, U.S. Patent No. 6,174,422; Zawacky et al, U.S. Patent Application Publication No.
  • useful dispersants and dispersing resins for cathodic electrodeposition coating compostions may be nonionic or cationic. If used, cationic dispersants or dispersing resins may be at least partially salted with an acid compatible with the electrocoat composition into which the zirconium dispersion will be added, including the same acid or acids used to salt the cationic binder resin of the electrocoat coating composition.
  • the zirconium silicate dispersion may be made by combining the dispersant or dispersing resin with the zirconium silicate, water, and, if necessary, salting acid to form a slurry.
  • the slurry may optionally include further resins, organic solvents, further solids such as fillers or pigments, and any customary additives, such as, for example, defoamers or wetting agents.
  • the zirconium silicate may typically have a primary particle size in a range of from about 1 ⁇ to about 10 ⁇ .
  • the slurry is generally subjected to mechanical shear to break apart solid particle agglomerates (e.g., agglomerates of zirconium silicate, optional pigments, optional fillers) and to wet the solid particle surfaces with the dispersant or dispersing resin, both to stabilize the dispersion and the prevent re-agglomeration of the particles.
  • concentration of zirconium silicate in the dispersion may vary widely, depending on factors such as the particular dispersants or dispersing resins used and in what concentrations, which fillers or pigments are included, if any, and in what
  • the slurry may be processed in an attritor, two-roll mill, or media mill such as a sandmill, ball mill, or pebble mill until the solid particles reach a desired particle size.
  • the zirconium silicate is included in a dispersion containing one or more pigments or one or more fillers.
  • Conventional pigments for electrocoat primers may also be incorporated into the electrocoat coating composition; nonlimiting examples of such pigments include corrosion-inhibiting pigments, colorants, extenders, conductive pigments, and magnetically shielding pigments.
  • suitable pigments and fillers include titanium dioxide, iron oxides, carbon black, magnesium silicate, aluminum silicate, barium sulfate, aluminum phosphomolybdate, strontium chromate, basic lead silicate, lead chromate, other anti-corrosion pigments, clay, bismuth oxide, vanadium oxide, manganese oxide, cobalt oxide, zinc oxide, strontium oxide, yttrium oxide, molybdenum oxide, zirconium oxide, lanthanum oxide, oxides of the lanthanide series of elements, and organic pigments such as metallized and non-metallized azo pigments such as lithol reds, rubine reds, and naphthol reds, oranges, and browns; quinacridone reds and violets, perylene reds, copper phthalocyanine blues and greens, carbazole violet, monoarylide and diarylide yellows, benzimidazolone yellows, tolyl orange, naphthol orange, and rhod
  • the pigment-to-resin weight ratio in the electrocoat bath can be important and should be preferably less than 50: 100, more preferably less than 40: 100, and usually about 10 to 30: 100.
  • pigment includes all dispersed solids, including not only color pigments but also the zirconium silicate and any filler particles included in the bath. Higher pigment-to- resin solids weight ratios have been found to adversely affect coalescence and flow.
  • the total amount of pigment and other solid particles is 10-40 percent by weight of the nonvolatile material in the bath. In some embodiments, the total amount of pigment and other solid particles is 15 to 30 percent by weight of the nonvolatile material in the bath.
  • the zirconium silicate dispersion may include a combination of pigments that may be added to the electrocoat coating composition at regular intervals as needed to maintain a desired pigment concentration in the bath regardless of the coating cure response or phosphate ion concentration.
  • the pigment dispersion containing zirconium silicate may be added as is customer for such pigment feeds when the pigment concentration in the electrocoat coating composition is depleted due to plating of materials from the coating composition.
  • the pigment-to-binder weight ratio in the electrocoat bath should usually be about 10 to 30 parts by weight pigment : 100 parts by weight binder.
  • the pigment is about 10-40 percent by weight of the nonvolatile material in the bath.
  • the pigment is about 15 to 30 percent by weight of the nonvolatile material in the bath.
  • the electrodeposition coating composition is treated by adding the zirconium silicate to the coating composition to overcome the effect on the cure catalyst of phosphate ions that enter it from the phosphate pretreatment process.
  • the concentration of phosphate ions in the coating composition can be monitored and the coating composition can be treated with the zirconium silicate when the concentration of phosphate ions in the coating
  • the zirconium silicate can be added to the coating composition after a decrease in extent of curing of the coating plated from the bath has been observed and, optionally, it has been determined that the concentration of phosphate ions in the coating composition is about 100 ppm or higher based on total bath weight.
  • zirconium silicate can be included in the bath as a prophylactic measure before any decrease in extent of cure is observed.
  • concentration of phosphate ions in the coating composition may be determined using an Inductively Coupled Argon Plasma Optical Emission Spectrometer ("ICP" or "ICAP-OES").
  • phosphate anions into the electrocoat coating composition interferes with the metal compound catalyst, particularly when the catalyst is a bismuth compound or a combination of bismuth compounds, but phosphate ions can also interfere with curing of the coating when the catalyst is a tin compound or other metal compound. While not wishing to be bound by theory, the zirconium silicate does not appear to act as a curing catalyst itself, but instead preferentially interacts or reacts with the phosphate anions to prevent their
  • an aqueous coating composition having a cathodically electrodepositable binder.
  • the binder has a resin with isocyanate- reactive functional groups and a blocked polyisocyanate crosslinker, capable of reacting with the principal resin during cure.
  • the coating composition further includes zirconium silicate and a catalyst consisting essentially of bismuth compounds and mixtures of bismuth compounds.
  • an electrodeposition coating composition binder includes a resin that has isocyanate-reactive functional groups and that is
  • Electrodepositable resins A variety of such resins are known, including without limitation, epoxy resins, polyesters, polyurethanes, and vinyl resins such as polyacrylate resins, and polybutadiene resins.
  • Many electrocoating applications including automotive applications, typically use an electrodepositable resin that is cathodic, i.e., it has salted basic groups (e.g., primary, secondary, or tertiary amine groups) or quaternary groups (e.g., ammonium, sulfonium, or phosphonium groups).
  • the article to be coated is the cathode.
  • the resin is an epoxy resin with amine groups.
  • Amino-epoxy resins may be prepared from resins having a plurality of epoxide groups, which may be reacted with one or more than polyfunctional, preferably difunctional, extender compounds and with one or more amine compounds.
  • Nonlimiting examples of resins with a plurality of epoxide groups include diglycidyl aromatic compounds such as the diglycidyl ethers of polyhydric phenols such as 2,2- bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3- methylphenyl)propane, 4,4'-dihydroxybenzophenone, dihydroxyacetophenones, 1,1- bis(4hydroxyphenylene)ethane, bis(4-hydroxyphenyl) methane, 1,1- bis(4hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl) propane, 1,4- bis(2-hydroxyethyl)piperazine, 2-methyl- 1 , 1 -bis(4-hydroxyphenyl)propane, bis-(2- hydroxynaphthyl)methane, l,5-dihydroxy-3-naphthalene, and other
  • diglycidyl ethers of bisphenol A and bisphenol A-based resins including diglycidyl ethers of bisphenol A and bisphenol A-based resins.
  • diglycidyl ethers of aliphatic diols including the diglycidyl ethers of 1 ,4- butanediol, cyclohexanedimethanols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polypropylene glycol, polyethylene glycol, poly(tetrahydrofuran), 1,3-propanediol, 2,2,4-trimethyl-l,3- pentanediol, 1,6-hexanediol, 2,2-bis(4-hydroxycyclohexyl) propane, and the like.
  • Diglycidyl esters of dicarboxylic acids can also be used as polyepoxides. Specific examples of compounds
  • cyclohexanediacetic acids cyclohexanediacetic acids, cylcohexanedicarboxylic acids, succinic acid, glutaric acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, and the like.
  • a polyglycidyl reactant may be used, preferably in a minor amount in combination with diepoxide reactant.
  • Novolac epoxies may be used as a
  • the novolac epoxy resin may be selected from epoxy phenol novolac resins or epoxy cresol novolac resins.
  • Other suitable higher- functionality polyepoxides are glycidyl ethers and esters of triols and higher polyols such as the triglycidyl ethers of trimethylolpropane, trimethylolethane, 2,6- bis(hydroxymethyl)-p-cresol, and glycerol; tricarboxylic acids or polycarboxylic acids.
  • Also useful as polyepoxides are epoxidized alkenes such as cyclohexene oxides and epoxidized fatty acids and fatty acid derivatives such as epoxidized soybean oil.
  • polyepoxides include, without limitation, polyepoxide polymers such as acrylic, polyester, polyether, and epoxy resins and polymers, and epoxy-modified polybutadiene, polyisoprene, acrylobutadiene nitrile copolymer, or other epoxy-modified rubber-based polymers that have a plurality of epoxide groups.
  • epoxy resin by reacting an excess of epoxide group equivalents with a modifying material, such as a polyol, a polyamine or a polycarboxylic acid, in order to improve the film properties.
  • a modifying material such as a polyol, a polyamine or a polycarboxylic acid
  • Useful epoxy resins of this kind have a weight average molecular weight, which can be determined by GPC, of from about 3000 to about 6000. Epoxy equivalent weights can range from about 200 to about 2500, and are preferably from about 500 to about 1500.
  • Suitable, nonlimiting examples of extender compounds include polycarboxylic acids, polyols, polyphenols, and amines having two or more amino hydrogens, especially dicarboxylic acids, diols, diphenols, and diamines.
  • suitable extenders include diphenols, diols, and diacids,
  • polycaprolactone diols and ethoxylated bisphenol A resins such as those available from BASF Corporation under the trademark MACOL®.
  • suitable extenders include, without limitation, carboxy- or amine-functional acrylic, polyester, polyether, and epoxy resins and polymers.
  • Still other suitable extenders include, without limitation, polyamines, including diamines such as ethylenediamine,
  • polyalkylenepolyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tripropylenetetramine, tetrapropylenepentamine,
  • monofunctional reactants include phenol, alkylphenols such as nonylphenol and dodecylphenol, other monofunctional, epoxide -reactive compounds such as dimethylethanolamine and monoepoxides such as the glycidyl ether of phenol, the glycidyl ether of nonylphenol, or the glycidyl ether of cresol, and dimer fatty acid.
  • Useful catalysts for the reaction of the polyepoxide resin with the extender and optional monofunctional reactant and for the reaction of an epoxide group of the resin with an aliphatic amine group of a compound with an tridentate amine ligand include any that activate an oxirane ring, such as tertiary amines or quaternary ammonium salts (e.g., benzyldimethylamine, dimethylaminocyclohexane, triethylamine, N-methylimidazole, tetramethyl ammonium bromide, and tetrabutyl ammonium hydroxide.), tin and/or phosphorous complex salts (e.g., (CH 3 ) 3 SnI, (CH ) 4 PI, triphenylphosphine, ethyltriphenyl phosphonium iodide, tetrabutyl phosphonium iodide) and so on.
  • tertiary amine catalysts may be preferred with some reactants.
  • the reaction may be carried out at a temperature of from about 100°C. to about 350°C. (in other embodiments 160°C to 250°C.) in solvent or neat.
  • Suitable solvents include, without limitation, inert organic solvent such as a ketone, including methyl isobutyl ketone and methyl amyl ketone, aromatic solvents such as toluene, xylene, Aromatic 100, and Aromatic 150, and esters, such as butyl acetate, n-propyl acetate, hexyl acetate.
  • Amino groups can be incorporated by reacting the polyglycidyl ethers of the polyphenols with amine or polyamines, such as by reaction of the polyepoxide resin with an extender having a tertiary amine group or by reaction with a mono functional reactant having an amine group.
  • Suitable, nonlimiting examples of extenders and monofunctional reactants having an amine group include diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, diisobutanolamine, diglycolamine, methylethanolamine, dimethylaminopropylamine, diethylaminopropylamine, dimethylaminoethylamine, N-aminoethylpiperazine, aminopropylmorpholine, tetramethyldipropylenetriamine, methylamine, ethylamine, dimethylamine, dibutylamine, ethylenediamine, diethylenetriamine,
  • Triethylenetetramine dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, methylbutylamine, methylethanolamine, aminoethylethanolamine, aminopropylmonomethylethanolamine, polyoxyalkylene amines, and compounds having a primary amine group that has been protected by forming a ketimine.
  • Quarternary ammonium groups may be incorporated, and are formed, for example, from a tertiary amine by salting it with an acid, then reacting the salting hydrogen with, e.g., a compound bearing an epoxide group to produce an ammonium group.
  • the epoxide groups on the epoxy resin are reacted with a compound comprising a secondary amine group and at least one latent primary amine.
  • the latent primary amine group is preferably a ketimine group. The primary amines are regenerated when the resin is emulsified.
  • the resin may have an amine equivalent weight of about 300 to about 3000, and more preferably of about 850 to about 1300.
  • Epoxy-modified novolacs can be used as a resin in the binder.
  • the epoxy-novolac resin can be capped in the same way as previously described for the epoxy resin.
  • Cationic polyurethanes and polyesters may also be used. Such materials may be prepared by endcapping with, for example, an aminoalcohol or, in the case of the polyurethane, the same compound comprising a saltable amine group previously described may also be useful.
  • Polybutadiene, polyisoprene, or other epoxy-modified rubber- based polymers can be used as the resin in the present invention. The epoxy-rubber can be capped with a compound comprising a saltable amine group.
  • Cationic acrylic resins may be used.
  • Acrylic polymers may be made cathodic by incorporation of amino-containing monomers, such as acrylamide, methacrylamide, ⁇ , ⁇ '-dimethylaminoethyl methacrylate tert-butylaminoethyl methacrylate.
  • epoxy groups may be incorporated by including an epoxy- functional monomer in the polymerization reaction.
  • Such epoxy-functional acrylic polymers may be made cathodic by reaction of the epoxy groups with amines according to the methods previously described for the epoxy resins.
  • polymerization may also include a hydroxyl-functional monomer.
  • Useful hydroxyl- functional ethylenically unsaturated monomers include, without limitation, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, the reaction product of methacrylic acid with styrene oxide, and so on.
  • Preferred hydroxyl monomers are methacrylic or acrylic acid esters in which the hydroxyl- bearing alcohol portion of the compound is a linear or branched hydroxy alkyl moiety having from 1 to about 8 carbon atoms.
  • the monomer bearing the hydroxyl group and the monomer bearing the group for salting may be polymerized with one or more other ethylenically unsaturated monomers.
  • Such monomers for copolymerization are known in the art.
  • Illustrative examples include, without limitation, alkyl esters of acrylic or methacrylic acid, e.g., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, amyl acrylate, amyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, dodecyl
  • polymerizable co-monomers include, for example, alkoxy ethyl acrylates and methacrylates, acryloxy acrylates and methacrylates, and compounds such as acrylonitrile, methacrylonitrile, acrolein, and methacrolein. Combinations of these are usually employed.
  • the molecular weight of a typical acrylic resin is usually in the range from about 2000 to about 50,000, and preferably from about 3000 to about 15,000.
  • the amino equivalent weight of the cationic resin can range from about 150 to about 5000, and preferably from about 500 to about 2000.
  • the hydroxyl equivalent weight of the resins, if they have hydroxyl groups, is generally between about 150 and about 2000, and preferably about 200 to about 800.
  • the resin can be emulsified in water in the presence of a salting compound.
  • a salting compound such as amine groups
  • the resin is salted with an acid
  • the resin is salted with a base.
  • the principal resin and the crosslinking agent are blended together before the resins are dispersed in the water.
  • Suitable neutralizing agents for the potentially cationic groups are organic and inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid, citric acid or sulfonic acids, such as amidosulfonic acids and alkanesulfonic acids, such as methanesulfonic acid, for example, more particularly formic acid, acetic acid or lactic acid.
  • the acid is used in an amount sufficient to neutralize enough of the amine groups of the principal resin to impart water-dispersibility to the resin.
  • the resin may be fully neutralized; however, partial neutralization is usually sufficient to impart the required water-dispersibility.
  • Partial neutralization means that at least one, but less than all, of the saltable groups on the resin are neutralized.
  • the resin is at least partially neutralized, it is meant that at least one of the saltable groups on the resin is neutralized, and up to all of such groups may be neutralized.
  • the degree of neutralization that is required to afford the requisite water-dispersibility for a particular resin will depend upon its chemical composition, molecular weight, and other such factors and can readily be determined by one of ordinary skill in the art through straightforward experimentation.
  • the saltable resin may be combined with an isocyanate
  • crosslinking agent before being dispersed in water.
  • the crosslinking agents are preferably selected from the group consisting of blocked polyisocyanates.
  • Nonlimiting examples of aromatic, aliphatic or cycloaliphatic polyisocyanates include diphenylmethane-4,4'-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), p- phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4,4'-diisocyanate, polymethylene polyphenylisocyanate, , 2- isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4'-diisocyanate, 1,3- bis(iso-cyanatomethyl)cyclohexane, diisocyanates derived from dimer fatty acids, as sold under the commercial designation DDI
  • Suitable polyisocyantes also include polyisocyanates derived from these that containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide, or uretdione groups.
  • Polyisocyanates containing urethane groups are obtained by reacting some of the isocyanate groups with polyols, such as
  • Diisocyanates used with preference are hexamethylene diisocyanate, isophorone diisocyanate, 2- isocyanatopropylcyclohexyl isocyanate, dicyclohexyl-methane 2,4'-diisocyanate, dicyclohexylmethane 4,4'-diisocyanate or l,3-bis(isocyanatomethyl)cyclohexane (BIC), diisocyanates derived from dimeric fatty acids, l,8-diisocyanato-4- isocyanatomethyloctane, 1 ,7-diisocyanato-4-isocyanatomethylheptane, 1 -isocyanato- 2-(3-isocyanatopropyl)cyclohexane, 2,4- and/or 2,6-tolylene diisocyan
  • the isocyanate groups are reacted with a blocking agent.
  • blocking agents examples include phenol, cresol, xylenol, epsilon- caprolactam, delta-valerolactam, gamma-butyrolactam, diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, alcohols such as methanol, ethanol, isopropanol, propanol, isobutanol, tert-butanol, butanol, glycol monoethers such as ethylene or propylene glycol monoethers, acid amides (e.g. acetoanilide), imides (e.g. succinimide), amines (e.g. diphenylamine), imidazole, urea, ethylene urea, 2- oxazolidone, ethylene imine, oximes (e.g. methylethyl ketoxime), and the like.
  • alcohols such as methanol, ethanol, isopropan
  • the binder is emulsified in water in the presence of a salting acid.
  • suitable acids include phosphoric acid, phosphonic acid, propionic acid, formic acid, acetic acid, lactic acid, or citric acid.
  • the salting acid may be blended with the binder, mixed with the water, or both, before the binder is added to the water.
  • the acid is used in an amount sufficient to neutralize at least enough of the ionizable resin groups to impart water-dispersibility to the binder.
  • the ionizable groups may be fully neutralized; however, partial neutralization is usually sufficient to impart the required water-dispersibility.
  • the resin is at least partially neutralized, we mean that at least one of the saltable groups of the binder is neutralized, and up to all of such groups may be neutralized.
  • the degree of neutralization that is required to afford the requisite water-dispersibility for a particular binder will depend upon its composition, molecular weight of the resins, weight percent of amine-functional resin, and other such factors and can readily be determined by one of ordinary skill in the art through straightforward
  • the binder emulsion is then used in preparing the first disclosed electrocoat coating composition (or bath) that further includes zirconium silicate and a catalyst consisting essentially of bismuth compounds and mixtures of bismuth compounds.
  • the bismuth compounds include bismuth lactate, bismuth dimethylpropionate, bismuth salicylate, bismuth acetate, bismuth methoxyacetate, bismuth oxalate, bismuth adipate, bismuth tartarate, bismuth propionate, bismuth butyrate, bismuth phthalate, bismuth citrate, bismuth gluconate, bismuth sulfamate, bismuth subnitrate (empirical formula 4(BiN0 3 (OH)) BiO(OH)), bismuth subsalicylate (empirical formula C 7 H 5 O 4 B1), bismuth naphthanate, bismuth methylmercaptothiodiazole, bismuth complex
  • the bismuth compound or compounds are typically used in amounts of about 0.2 to about 5 percent by weight, preferably about 0.5 to about 3 percent by weight, and more preferably about 2 to about 2.5 percent by weight, with the percent by weight in each case being based on total nonvolatile binder weight.
  • Bismuth fatty acid salts are often not preferred in an electrocoat coating composition because they produce oily exudations that can disrupt the film, while inorganic bismuth compounds may be more difficult to disperse.
  • the electrocoat coating composition further includes zirconium silicate.
  • the zirconium silicate may be included by adding an aqueous dispersion of zirconium silicate as already described.
  • the electrocoat coating composition usually contains one or more pigments or fillers.
  • the aqueous dispersion of zirconium silicate further includes one or more fillers or pigments and may further include the bismuth compound or compounds.
  • the pigments or fillers and the bismuth compound or compounds are added separately in the case where the aqueous dispersion of zirconium silicate does not include them; the pigments or fillers and the bismuth compound or compounds may be added as aqueous dispersions also, which may be prepared in the same way as the aqueous dispersion of zirconium silicate.
  • the electrocoat coating composition may include further desired materials such as coalescing aids, antifoaming aids, plasticizers, and other additives.
  • plasticizers include ethylene or propylene oxide adducts of nonyl phenols, bisphenol A, cresol, or other such materials, or polyglycols based on ethylene oxide and/or propylene oxide.
  • coalescing solvents include alcohols, glycol ethers, polyols, and ketones.
  • coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, phenyl ether of propylene glycol, monoalkyl ethers of ethylene glycol such as the monomethyl, monoethyl, monopropyl, and monobutyl ethers of ethylene glycol or propylene glycol; dialkyl ethers of ethylene glycol or propylene glycol such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; butyl carbitol; diacetone alcohol.
  • the amount of coalescing solvent is not critical and is generally up to 15 percent by weight, preferably about 0.5 to 5 percent by weight based on total weight of the resin solids. Plasticizers can be used at levels of up to 15 percent by weight resin solids.
  • the electrodeposition coating compositions can contain optional ingredients such as dyes, flow control agents, anticrater additives, plasticizers, wetting agents, surfactants, UV absorbers, HALS compounds, and other light stabilizers, antioxidants, defoamers, thermally curable reactive diluents, antioxidants, emulsifiers, slip additives, adhesion promoters, waxes, siccatives, biocides, matting agents, and so on, in effective amounts.
  • surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as AMINE C® acetylenic alcohols such as those available from Air Products and Chemicals under the tradename SURFYNOL®.
  • Surfactants and wetting agents when present, typically amount to up to 2 percent by weight resin solids.
  • the electrocoat coating composition may be produced by mixing and homogenizing the above-described constituents using typical and known mixing methods and apparatus such as stirred tanks, agitator mills, extruders, compounders, Ultraturrax, inline dissolvers, static mixers, micromixers, toothed-wheeled dispersers, pressure release nozzles and/or micro fluidizers.
  • typical and known mixing methods and apparatus such as stirred tanks, agitator mills, extruders, compounders, Ultraturrax, inline dissolvers, static mixers, micromixers, toothed-wheeled dispersers, pressure release nozzles and/or micro fluidizers.
  • an aqueous coating composition again having a cathodically electrodepositable binder, the binder has a principal resin and a blocked polyisocyanate crosslinker as already described, in which the coating composition includes zirconium silicate and at least one bismuth compound other than bismuth hydroxide.
  • the coating composition is free of tin compounds and free of bismuth hydroxide.
  • This coating composition may be made in the same way as the first- described electrocoat coating composition and may include catalysts other than bismuth and tin catalysts.
  • the at least one bismuth compound other than bismuth hydroxide may again be a catalyst for the curing reaction of an electrocoat coating electrodeposited from the coating composition
  • a coating of one of the disclosed electrocoat coating compositions is electrodeposited onto a metallic substrate.
  • the substrate may be, as some nonlimiting examples, cold-rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, GAL V ANNEAL®
  • the metallic substrate is placed in the electrocoat coating composition, with the metallic substrate connected as one electrode in an electrical circuit, and a coating is electrodeposited onto the metallic substrate by passing a current through the electrocoat coating composition causing a coating layer to deposit onto the electrically conductive substrate.
  • the electrodeposition coating composition may be applied preferably to a dry film thickness of 10 to 35 ⁇ .
  • the article coated with the composition of the invention may be a metallic automotive part or body.
  • the electrically conductive substrate is used as the cathode.
  • the coated article is removed from the electrocoat coating composition bath and rinsed with deionized water.
  • the coating may be cured under appropriate conditions, for example by baking at from about 275° F to about 375° F for between about 15 and about 60 minutes, before applying an additional coating layer over the
  • One or more additional coating layers may be applied over the electrocoat layer.
  • a single layer topcoat is also referred to as a topcoat enamel.
  • the topcoat is typically a basecoat that is overcoated with a clearcoat layer.
  • a primer surfacer and the topcoat enamel or basecoat and clearcoat composite topcoat may be waterborne, solventbome, or a powder coating, which may be a dry powder or an aqueous powder slurry.
  • the composite coating of the invention may have, as one layer, a primer coating layer, which may also be termed a primer-surfacer or filler coating layer.
  • the primer coating layer can be formed from a solventbome composition, waterbome composition, or powder composition, including powder slurry
  • the primer composition preferably has a binder that is thermosetting, although thermoplastic binders are also known. Suitable thermosetting binders may have self-crosslinking polymers or resins, or may include a crosslinker reactive with a polymer or resin in the binder.
  • suitable binder polymers or resins include acrylics, polyesters, and polyurethanes. Such polymers or resins may include as functional groups hydroxyl groups, carboxyl groups, anhydride groups, epoxide groups, carbamate groups, amine groups, and so on.
  • crosslinkers reactive with such groups are aminoplast resins (which are reactive with hydroxyl, carboxyl, carbamate, and amine groups), polyisocyanates, including blocked polyisocyanates (which are reactive with hydroxyl group and amine groups), polyepoxides (which are reactive with carboxyl, anhydride, hydroxyl, and amine groups), and polyacids and polyamines (which are reactive with epoxide groups).
  • aminoplast resins which are reactive with hydroxyl, carboxyl, carbamate, and amine groups
  • polyisocyanates including blocked polyisocyanates (which are reactive with hydroxyl group and amine groups)
  • polyepoxides which are reactive with carboxyl, anhydride, hydroxyl, and amine groups
  • polyacids and polyamines which are reactive with epoxide groups
  • the primer coating composition applied over the electrocoat primer may then be cured to form a primer coating layer.
  • the electrocoat primer may be cured at the same time as the primer coating layer in a process known as "wet-on- wet" coating or may be cured before the primer coating composition is applied.
  • a topcoat composition may be applied over the electrocoat layer or primer coating layer and, preferably, cured to form a topcoat layer.
  • the electrocoat layer or primer layer is coated with a topcoat applied as a color-plus-clear (basecoat-clearcoat) topcoat.
  • basecoat-clearcoat topcoat an underlayer of a pigmented coating, the basecoat, is covered with an outer layer of a transparent coating, the clearcoat.
  • Basecoat-clearcoat topcoats provide an attractive smooth and glossy finish and generally improved performance. Typically, the basecoat and the clearcoat are cured at the same time.
  • Crosslinking compositions are preferred as the topcoat layer or layers. Coatings of this type are well-known in the art and include waterborne compositions, solventborne compositions, and powder and powder slurry
  • compositions are compositions.
  • Polymers known in the art to be useful in basecoat and clearcoat compositions include, without limitation, acrylics, vinyls, polyurethanes,
  • topcoat binders polycarbonates, polyesters, alkyds, and polysiloxanes. Acrylics and polyurethanes are among preferred polymers for topcoat binders.
  • Thermoset basecoat and clearcoat compositions are also preferred, and, to that end, preferred polymers comprise one or more kinds of crosslinkable functional groups, such as carbamate, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, acetoacetate, and so on.
  • the polymer may be self-crosslinking, or, preferably, the composition may include a crosslinking agent such as a polyisocyanate or an aminoplast resin. Examples of suitable topcoat compositions are disclosed, for example, in U.S. Patents No
  • the further coating layers can be applied to the electrocoat coating layer according to any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like.
  • the further coating layer or layers are preferably applied by spray coating, particularly electrostatic spray methods. Coating layers of one mil or more are usually applied in two or more coats (passes), separated by a time sufficient to allow some of the solvent or aqueous medium to evaporate, or "flash," from the applied layer.
  • the flash may be at ambient or elevated temperatures, for example, the flash may use radiant heat.
  • the coats as applied can be from 0.5 mil up to 3 mils dry, and a sufficient number of coats are applied to yield the desired final coating thickness.
  • a primer layer may be cured before the topcoat is applied.
  • the cured primer layer may be from about 0.5 mil to about 2 mils thick, preferably from about 0.8 mils to about 1.2 mils thick.
  • Color-plus-clear topcoats are usually applied wet-on-wet.
  • the compositions are applied in coats separated by a flash, as described above, with a flash also between the last coat of the color composition and the first coat the clear.
  • the two coating layers are then cured simultaneously.
  • the cured basecoat layer is 0.5 to 1.5 mils thick
  • the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils, thick.
  • the primer layer and the topcoat can be applied "wet- on-wet.”
  • the primer composition can be applied, then the applied layer flashed; then the topcoat can be applied and flashed; then the primer and the topcoat can be cured at the same time.
  • the topcoat can include a basecoat layer and a clearcoat layer applied wet-on-wet.
  • the primer layer can also be applied to an uncured electrocoat coating layer, and all layers cured together.
  • the coating compositions described are preferably cured with heat.
  • Curing temperatures are preferably from about 70°C to about 180°C, and particularly preferably from about 170°F to about 200°F for a topcoat or primer composition including an unblocked acid catalyst, or from about 240°F to about 275 °F for a topcoat or primer composition including a blocked acid catalyst.
  • Typical curing times at these temperatures range from 15 to 60 minutes, and preferably the temperature is chosen to allow a cure time of from about 15 to about 30 minutes.
  • the coated article is an automotive body or part.
  • Dispersions A-D were prepared with the following compositions. Parts are by weight.
  • the phosphate solution is a commercial phosphate treatment obtained from automotive assembly plant. 3. 40% Aqueous dispersion of a lactic acid-salted amine-functional epoxy resin having 27% by weight of an acid salted, amine-functional epoxy resin, 12% by weight of a blocked isocyanate crosslinker, and 2% by weight of a plasticizer.

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Abstract

L'invention concerne une composition de revêtement par électrodéposition contaminée par des ions phosphate qui est traitée par addition de silicate de zirconium à la composition de revêtement. Des compositions aqueuses de revêtement par électrodéposition comprenant (1) un composé de bismuth dépourvu de composés d'étain et dépourvu d'hydroxyde de bismuth ou (2) ayant un catalyseur consistant essentiellement en un élément choisi dans l'ensemble consistant en composés de bismuth et mélanges de ceux-ci comprennent également du silicate de zirconium.
PCT/US2013/061399 2012-11-09 2013-09-24 Procédé pour améliorer le durcissement d'un revêtement pour un article revêtu dans une composition de revêtement par électrodéposition contaminée par du phosphate et composition de revêtement par électrodéposition WO2014074234A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP13776618.4A EP2917293B1 (fr) 2012-11-09 2013-09-24 Procédé pour améliorer le durcissement d'un revêtement pour un article revêtu dans une composition de revêtement par électrodéposition contaminée par du phosphate et composition de revêtement par électrodéposition
CA2883990A CA2883990A1 (fr) 2012-11-09 2013-09-24 Procede pour ameliorer le durcissement d'un revetement pour un article revetu dans une composition de revetement par electrodeposition contaminee par du phosphate et composition de revetement par electrodeposition
CN201380057953.5A CN104769051B (zh) 2012-11-09 2013-09-24 提高由受磷酸盐离子污染的电涂涂料组合物涂布的制品的涂层固化的方法和电涂涂料组合物
JP2015541766A JP6375304B2 (ja) 2012-11-09 2013-09-24 リン酸塩汚染された電着塗装塗料組成物で被覆された物品の塗装硬化性の改良方法および電着塗装塗料組成物
MX2015003384A MX2015003384A (es) 2012-11-09 2013-09-24 Metodo para mejorar el curado del revestimiento para articulo revestido en composicion de revestimiento para electrorrevestimiento, contaminada con fosfato, y composicion de revestimiento para electrorrevestimiento.
US14/441,430 US20150267315A1 (en) 2012-11-09 2013-09-24 Method For Improving Coating Cure For Article Coated In Phosphate-Contaminated Electrocoat Coating Composition And Electrocoat Coating Composition

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US61/724,541 2012-11-09

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WO2016130656A1 (fr) * 2015-02-10 2016-08-18 Valspar Sourcing, Inc. Nouveau système d'électrodéposition
WO2017178618A1 (fr) * 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Traitement de structure de transport pour supprimer le transfert de phosphates, lié à l'équipement, dans une séquence de traitement de laquage par immersion
EP3845612A1 (fr) * 2019-12-30 2021-07-07 Axalta Coating Systems GmbH Composition d'électrodéposition à faible densité possédant une meilleure puissance de lancement
WO2021198866A1 (fr) * 2020-03-31 2021-10-07 Kansai Nerolac Paints Limited Composition bleue de revêtement par électrodéposition cathodique (ced)
WO2021239264A1 (fr) * 2020-05-25 2021-12-02 Basf Coatings Gmbh Matériau d'électrodéposition contenant du bismuth présentant une activité catalytique améliorée
EP4095202A1 (fr) * 2021-05-28 2022-11-30 Axalta Coating Systems GmbH Composition d'électrodéposition
RU2822390C1 (ru) * 2020-05-25 2024-07-04 БАСФ Коатингс ГмбХ Содержащий висмут материал для нанесения покрытия электроосаждением с улучшенной каталитической активностью

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BR112018016379A2 (pt) * 2016-02-10 2018-12-18 Swimc Llc composição em pó, e, método
BR112018016204A2 (pt) * 2016-02-10 2018-12-18 Swimc Llc composição de revestimento, artigo revestido resistente à corrosão, e, método para fabricação de um artigo revestido resistente à corrosão.
CN107974690B (zh) * 2017-11-24 2019-10-11 盐城工学院 电极及其制备方法和应用以及制备甲酸的方法
US20220380674A1 (en) * 2021-05-18 2022-12-01 Ticona Llc Photoplethysmographic Sensor Containing A Polymer Composition

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EP2917293B1 (fr) 2017-11-15
JP2015533921A (ja) 2015-11-26
CN104769051A (zh) 2015-07-08
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US20150267315A1 (en) 2015-09-24
MX2015003384A (es) 2015-06-05

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